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Cyclobutyne ligands. 2. Reactions of the cyclobutyne triosmium complex Os[sub 3](CO)[sub 9]([mu][sub 3]-[eta][sup 2]-C[sub 2]CH[sub 2]CH[sub 2])([mu]-SPh)([mu]-H) with diphenylacetylene

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00033a012· OSTI ID:5576543
; ; ;  [1]
  1. Univ. of South Carolina, Columbia, SC (United States)

The reaction of the triosmium complex Os[sub 3](CO)[sub 9]([mu][sub 3]-[eta][sup 2]-C[sub 2]CH[sub 2])([mu]-SPh) ([mu]-H) (1) with diphenylacetylene at 97[degree]C resulted in the formation of three products: the known compound Os[sub 2](CO)[sub 6]([mu]-[eta][sup 2]-C=CHCH[sub 2]CH[sub 2])([mu]- SPh) (2) (11% yield) and two new compounds Os[sub 3](CO)[sub 7][[mu]-C(Ph)(H)C(Ph)][[mu]-C(Ph)CCH[sub 2]CH[sub 2]] ([mu][sub 3]-S) (3) (28% yield) and Os[sub 3](CO)[sub 7]([mu]-C(Ph)C(Ph)CCC-H[sub 2]CH[sub 2]) ([mu]-SPh)([mu]-H) (4) (25% yield). Both new compounds were characterized by single-crystal X-ray diffraction analysis. Compound 3 contains a [sigma]-[pi] coordinated phenylcyclobutenyl ligand formed by the transfer of the phenyl group from the thiolate ligand to the cyclobutyne ligand and a [sigma]-[pi] coordinated 1,2-diphenylvinyl ligand formed by the insertion of one molecule of PhC[triple bond]CPh into the metal-hydrogen bonds. Compound 4 contains a metallacycle formed by the coupling of one molecule of PhC[triple bond]CPh to the cyclobutyne ligand. Crystal data: for 3a, space group = P2[sub 1]n, a = 17.401(3) A, b = 7.981(1) A, c = 22.304(4) A, [beta] = 100.26(1)[degrees], Z = 4, 3048 reflections, R = 0.030; for 4, space group = P[bar 1], a = 11.815(2) A, b = 12.260(2) A, c = 11.492(3) A, [alpha] = 102.91(2)[degrees], [beta] = 110.86(1)[degrees], [gamma] = 92.44(1)[degrees], Z = 2,3274 reflections, R = 0.043 17 refs., 2 figs., 7 tabs.

OSTI ID:
5576543
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:9; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English